Light weight proppant with improved strength and methods of making same

Patent metadata

Field	Value
Publication number	US-2016222281-A1
Application number	US-201615003211-A
Country	US
Kind code	A1
Filing date	Jan 21, 2016
Priority date	Oct 13, 2010
Publication date	Aug 4, 2016
Grant date	—

Abstract

Methods are described to make strong, tough, and/or lightweight glass-ceramic composites having a crystalline phase and an amorphous phase generated by viscous reaction sintering of a complex mixture of oxides and other materials. The present invention further relates to strong, tough, and lightweight glass-ceramic composites that can be used as proppants and for other uses.

First claim

What is claimed is:

1 . A proppant comprising a sintered body, wherein said sintered body comprises at least one crystalline phase, at least one amorphous phase, and substantially spherical microspheres and/or pores uniformly distributed in said sintered body.

2 . The proppant of claim 1 , wherein said crystalline phase is continuous and uniformly distributed throughout said sintered body.

3 . The proppant of claim 1 , wherein said crystalline phase is discontinuous and uniformly distributed throughout said sintered body.

4 . The proppant of claim 1 , wherein said pores have a smooth, glassy interior surface.

5 . The proppant of claim 1 , further comprising a template, wherein said sintered body encapsulates said template.

6 . The proppant of claim 5 , wherein said template is a sphere.

7 . The proppant of claim 5 , wherein said template is a hollow sphere.

8 . The proppant of claim 5 , wherein said template is a cenosphere.

9 . The proppant of claim 5 , wherein said sintered body encapsulates said template.

10 . The proppant of claim 5 , wherein said template comprises whiskers and at least one amorphous phase.

11 . The proppant of claim 1 , wherein said proppant has at least one of the following characteristics:
a. an overall diameter of from about 90 microns to about 2,000 microns; b. a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.5; c. a crush strength of about 1400 psi or greater; d. a specific gravity of from about 1.0 to about 3.0; e. a porosity of from about 1% to about 70% by weight; f. at least 90% (by distribution) of the microspheres and/or pores having a pore size of from about 0.1 μm to about 10 μm, and g. microspheres and/or pores have a smooth, glassy interior surface, and h. at least 80% (by distribution) of proppant pores are not in contact with each other.

12 . A method to prop open subterranean formation fractures comprising introducing a proppant formulation comprising the proppant of claim 1 into a subterranean formation.

13 . A method of treating a subterranean producing zone penetrated by a well bore comprising the steps of:
a. preparing or providing a treating fluid that comprises a fluid, energized fluid, foam, or a gas carrier having the proppant of claim 1 suspended therein, and b. pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

14 . The method of claim 13 , wherein said treating fluid is a fracturing fluid and said particles are deposited in fractures formed in said subterranean producing zone.

15 . The method of claim 13 , wherein said treating fluid is a gravel packing fluid and said particles are deposited in said well bore adjacent to said subterranean producing zone.

16 . The proppant of claim 1 comprising a sintered sphere having a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.4, and wherein said sphere comprises a) at least one crystalline phase and b) at least one amorphous phase, c) a plurality of microspheres and, optionally, d) ceramic whiskers, wherein said sintered sphere has a diameter of from about 90 microns to 2,500 microns, and said sintered sphere has a specific gravity of from 0.8 g/cc to about 3.8 g/cc, and said proppant has a crush strength of from about 1,000 psi or greater, and wherein said proppant includes one or more of the following characteristics:
1) said crystalline phase is present in an amount of at least 30% by weight, based on the weight of the proppant;
2) said amorphous phase is present in an amount of at least 10% by weight, based on the weight of the proppant;
3) said proppant having a porosity from about 1% to 70% by weight where

porosity


(
%
)

=

100
-

(

SG
m

SG
t

)

×
100

 and
SG m =measured specific gravity and
SG t =theoretical specific gravity;

4) said proppant having a porosity from about 5% to 50% by weight;
5) said proppant having a porosity from about 3% to 20% by weight;
6) said proppant having a porosity from about 4% to 16% by weight;
7) said proppant having a specific gravity of from 1.6 to 1.8 with a crush strength of at least 2000 psi;
8) said proppant having a specific gravity of from 1.8 to 2 with a crush strength of at least 3000 psi;
9) said proppant having a specific gravity of from 2 to 2.1 with a crush strength of at least 5,000 psi;
10) said proppant having a specific gravity of from 2.25 to 2.35 with a crush strength of at least 8,000 psi;
11) said proppant having a specific gravity of from 2.5 to 3.2 with a crush strength of at least 18,000 psi;
12) said proppant having a specific gravity of from 2.5 to 3.2 with a crush strength of at least 30,000 psi;
13) said proppant having a combined clay amount and cristobalite amount of less than 20% by weight of proppant;
14) said proppant having a free alpha-alumina content of at least 5% by weight of said proppant;
15) said proppant having an HF etching weight loss of less than 35% by weight of said proppant;
16) said proppant having said microspheres present as hollow glass microspheres having a particle size distribution, d as , of from about 0.5 to about 2.7, wherein, d as ={(d a90 −d a10 )/d a50 } wherein d a10 is a particle size wherein 10% of the particles have a smaller particle size, d a50 is a median particle size wherein 50% of the particles have a smaller particle size, and d a90 is a particle size wherein 90% of the particle volume has a smaller particle size;
17) said proppant having microspheres present wherein said microspheres are uniformly present in said proppant or in a layered region of said proppant;
18) said optional ceramic whiskers have an average length of less than 5 microns;
19) said optional ceramic whisker have an average width of less than 0.35 micron;
20) said optional ceramic whiskers have a whisker length distribution, d as , of about 8 or less, wherein, d as ={(d a90 −d a10 )/d a50 } wherein d a10 is a whisker length wherein 10% of the whiskers have a smaller length, d a50 is a median whisker length wherein 50% of the whiskers have a smaller whisker length, and d a90 is a whisker length wherein 90% of the whiskers have a smaller whisker length;
21) said optional ceramic whiskers are present in an amount of from 5% to 60% by weight of said proppant;
22) said proppant has a combined clay amount and cristobalite amount of less than 20% by weight of proppant and said mullite whiskers are present in an amount of 60% or more by weight of said proppant;
23) said proppant has a uniform composition comprised of both crystalline and amorphous materials that extend from the inner portions of the proppant out through the surface; and/or,

Assignees

• Halliburton Energy Services Inc

Inventors

• Chatterjee Dilip
• Pham Jody
• Wu Shanghua
• Xie Yuming
• Coker Christopher E

Classifications

• C09K8/80 Primary

  Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open · CPC title

• E21B43/267

  reinforcing fractures by propping · CPC title

• E21B43/04

  Gravelling of wells · CPC title

• C04B2235/528

  Spheres · CPC title

• C04B38/009

  Porous or hollow ceramic granular materials, e.g. microballoons (C04B18/027, C04B20/002 take precedence) · CPC title